Concentrated Dye Solution

ABSTRACT

Concentrated aqueous dye solutions comprising one or more cationizable dyes, an organic acid and water and their use for dyeing and/or printing organic substrates and for producing inkjet printing inks.

The present invention relates to a concentrated storage-stable aqueousdye solution and more particularly to a concentrated storage-stableaqueous dye solution without any solubilizer content. The inventionfurther relates to the use of the present invention's concentrated dyesolution, if appropriate after dilution with water, especially fordyeing and printing paper, including card and board.

Industrial dyeing and printing is typically carried out in an aqueousmedium. Pulverulent dyes must accordingly first be dissolved in mostlywarm or hot water to be usable for printing and dyeing.

Metering systems developed for this purpose utilize weighing orvolumetric methods to control the metered addition of dyes and theyrequire stable dye solutions instead of powders and granules.

Such dye solutions have the advantage that they are easily meterable, donot dust and do not require costly dissolving operations.

The solutions should possess optimum stability, so that they do notprecipitate during transportation or storage. Typically, they should bestable for a prolonged period between nought and five degrees Celsius,but also at around 50° C. Similarly, frozen solutions shall be stableafter pouring and should not present any stability problems duringpumping. Precipitates can cause disruptions in pumping or meteringsystems and lead to unacceptable machine shutdowns and costly cleaningand maintenance.

One problem of known aqueous dye solutions is the large amounts of addedsolubilizers, which lead to a high carbon content in the dyehouse orpaper mill effluence. This leads to effluence of high total organiccarbon (TOC) and chemical oxygen demand (COD), and hence causes highwater-treating costs. It is accordingly an object of the presentinvention to provide a concentrated aqueous dye solution for which thedye does not have to be isolated and dried (high energy costs!) andwhich includes few or no solubilizers.

It has now been found that a concentrated aqueous dye solution withoutaddition of solubilizers is stable when the dye is not isolated butultrafiltered to concentrate it and free it of reaction-basedsolubilizers (such as 1-methyl-2-pyrrolidone or dimethylacetamide).

The concentrated aqueous dye solutions of the present invention compriseone or more cationizable dyes, an organic acid and water.

The present invention's concentrated aqueous dye solutions in a furtherpreferred embodiment comprise dyes of the formula (I)

where

-   -   each A is independently —NH— or —O—,    -   B is a polyvalent group or atom,    -   n′ and n″ are natural numbers and the sum total of n′ and n″ is        ≧2,    -   m is a natural number ≧0,    -   CC is a group having the formula (c₁) or (c₂)        where    -   each R₁₀ is independently H; C₁₋₄alkyl; C₅₋₆cycloalkyl; phenyl,        benzyl or phenylethyl,    -   each R₁₀′ is independently H; —OH or C₁₋₄alkyl    -   each T₁ is independently H; —CN; —COOR₁₅; CONR₁₆R₁₇;    -   G is H; —R₁₁NHR₁₂ or —R₁₁NR₁₃R₁₄ where    -   R₁₁ is C₁₋₆alkylene or C₂₋₆alkenylene,    -   R₁₂ and R₁₃ are independently H; unsubstituted C₁₋₆alkyl;        C₂₋₆alkyl substituted by OH, CN or halogen; phenyl-C₁₋₃alkyl        where the phenyl radical is optionally singly, doubly or triply        substituted by substituents selected from the group consisting        of chlorine, C₁₋₄alkyl or C₁₋₄alkoxy; unsubstituted        C₅₋₆cycloalkyl or C₅₋₆cycloalkyl singly, doubly or triply        substituted by C₁₋₄alkyl groups,    -   R₁₄ has meaning as for R₁₂ or R₁₃ or a hydrogen atom,    -   R₁₅ is C₁₋₆alkyl radical or phenyl-C₁₋₃alkyl radical,    -   R₁₆ and R₁₇ are independently H or a C₁₋₄alkyl radical,    -   R₁₈ is in each occurrence independently H; a C₁₋₄alkyl radical;        —NR₁₆R₁₇—(CH₂)₂₋₄—NR₁₆R₁₇ or —CONR₁₆R₁₇,    -   R₁₉ is a C₁₋₄alkyl radical or a hydroxy-C₁₋₄alkyl radical,    -   R₂₀ is —S— or —O—,    -   R₂₁ is a hydrogen atom or a C₁₋₄alkyl radical, and    -   An⁻ is a non-coloured anion,        with the conditions that        (i) the sum total of n′, n″ and m is less than the number of        valences of B,        (ii) when the sum total of n′ and n″=2, then m is ≧1,        (iii) when the sum total of n′ and n″=3 and A=NH, then m is ≧1        an organic acid and water.

The present invention's storage-stable high-concentration solutions ofdyes of the formula (I) may also comprise a plurality of different dyeswhose formulae come within the formula (I).

In preferred dyes of the formula (I), T₁ is a substituent of the formula

In further preferred dyes, the CC group is a substituent of the formula

Preferably B is a group B′C[(CH₂)₀₋₄]₁₋₄ or B is one of the groups—[—(CH₂)₁₋₄—O—(CH₂)₁₋₄]₄C or [—(CH₂)₁₋₃—O—(CH₂)₁₋₃—O—(CH₂)₁₋₃]₄C or[—(CH₂)₁₋₂—O—(CH₂)₁₋₂—O—(CH₂)₁₋₂—O—(CH₂)₁₋₂]₄C or[(—CH₂)₁₋₄]₂N(CH₂)₁₋₄N[(—CH₂)₁₋₄]₂. It is particularly preferable for Bto be a carbon atom.

Particularly preferred compounds of the formula of the formula (I) havethe formula (Ia)

where

-   -   CC is a substituent of the formula (c₁) or (c₂) and    -   n″ is 1, 2, 3 or 4, with the conditions that    -   when n″=1, then B″ is C(CH₂OH)₃,    -   when n″=2, then B″ is C(CH₂OH)₂,    -   when n″=3, then B″ is C(CH₂OH),    -   when n″=4, then    -   B″ is C; [—(CH₂)₁₋₄—O—(CH₂)₁₋₄]₄C;        [—(CH₂)₁₋₃—O—(CH₂)₁₋₃—O—(CH₂)₁₋₃]₄C;        [—(CH₂)₁₋₂—O—(CH₂)₁₋₂—O—(CH₂)₁₋₂—O—(CH₂)₁₋₂]₄C or        [(—CH₂)₁₋₄]₂N(CH₂)₁₋₄N[(—CH₂)₁₋₄]₂.

Compounds of the formula of the formula (Ia) are very special wherein CCis a substituent of the formula (c₁) or (C₂) and

-   -   n″ is 1, 2, 3 or 4, with the conditions that    -   when n″=1, then B″ is C(CH₂OH)₃    -   when n″=2, then B″ is C(CH₂OH)₂,    -   when n″=3, then B″ is C(CH₂OH),    -   when n″=4, then B″ is C.

The present invention's storage-stable high-concentration solutions ofdyes of the formula (I) have a formula (I) dye content of up to 40% byweight of dye reckoned on the total weight of the solution. Preferreddye solutions have a dye content in the range from 5% to 40% by weightof dye or a dye content in the range from 10% to 35% by weight of dyeand most preferably a dye content in the range from 15% to 25% by weightof dye.

The level of organic acids in the present invention's storage-stablehigh-concentration solutions of dyes of the formula (I) is between 0.5%by weight and 25% by weight reckoned on the total weight of thesolution. Preferred dye solutions comprise from 1% to 15% by weight ofadded organic acids or from 2% to 10% by weight of added organic acidsand most preferably from 3% to 7% by weight of added organic acids.

Preferred organic acids are acids of the formula A(—COOH)_(n) where A isC₁₋₁₂-alkanyl or C₁₋₁₂-alkenyl which may each be interrupted by nitrogenatoms and or oxygen atoms and which may each be additionally substitutedby hydroxyl or NR′R″ (where R′ and R″ are independently C₁₋₆-alkanyl orC₁₋₆-alkenyl or C₁₋₆-hydroxyalkanyl or C₁₋₆-hydroxyalkenyl, orunsubstituted phenyl or hydroxyl- or sulphur- or C₁₋₁₈-alkanyl- orC₁₋₁₈-alkenyl-substituted phenyl) and with n as a natural number of 1, 2or 3. n is preferably =1 or 2 and more preferably =1.

Particular preference is given to formic acid, acetic acid, malonicacid, propionic acid, lactic acid, tartaric acid, benzoic acid, succinicacid. Acetic acid is the most preferred organic acid. These acids willbe present in a partially deprotonated (dissociated) state, as would beexpected from their pK value and from the pH value of the dye solution.

Examples of preferred non-coloured anions are chlorides, bromides,sulphates, bisulphates, methosulphates, aminosulphonates, perchlorates,benzenesulphonates, oxalates, malonates, maleates, acetates,propionates, lactates, succinates, tartrates, malates,methanesulphonates and benzoates. But also complex anions such as forexample zinc chloride double salts and anions of boric acid, citricacid, glycolic acid, diglycolic acid and adipic acid or additionproducts of orthoboric acid with polyalcohols having at least one cisdiol group. These anions may of course also be exchanged, for example bymeans of ion exchangers or customary precipitation reactions. The ionscan also be exchanged by diafiltration or ultrafiltration. The halideschloride and bromide are particularly preferred anions and chloride ismost preferred.

In principle, the salts of the added organic acids can likewise performthe anion function. In a particularly preferred embodiment, the anionsare chlorides and the added organic acid is acetic acid.

Preferred dye solutions according to the present invention consist of upto 40% by weight of dye, from 0.5% to 25% by weight of the organic acidand, made up to 100% by weight, of water, but especially of 10% to 35%by weight of dye, from 1% to 15% by weight of the organic acid and, madeup to 100% by weight, of water, with especially preferred dye solutionsconsisting of 15% to 25% by weight of dye, from 2% to 10% by weight ofthe organic acid and, made up to 100% by weight, of water.

Particularly preferred dye solutions according to the present inventionconsist of up to 40% by weight of dye as chloride, from 0.5% to 25% byweight of the organic acid and, made up to 100% by weight, of water, butespecially of 10% to 35% by weight of dye as chloride, from 1% to 15% byweight of the organic acid and, made up to 100% by weight, of water,with especially preferred dye solutions consisting of 15% to 25% byweight of dye as chloride, from 2% to 10% by weight of the organic acidand, made up to 100% by weight, of water.

Very particularly preferred dye solutions according to the presentinvention consist of up to 40% by weight of dye as chloride, from 0.5%to 25% by weight of acetic acid and, made up to 100% by weight, ofwater, but especially of 10% to 35% by weight of dye as chloride, from1% to 15% by weight of acetic acid and, made up to 100% by weight, ofwater, with especially preferred dye solutions consisting of 15% to 25%by weight of dye as chloride, from 2% to 10% by weight of acetic acidand, made up to 100% by weight, of water.

The invention also provides a process for producing the invention's dyesolutions which is characterized in that an aqueous solution orsuspension of at least one crude cationic dye is pressed through asemipermeable membrane by applying a pressure to remove salts andsynthesis by-products having molecular weights below 500 and some water.

In a preferred embodiment, the permeate is continuously orintermittently replaced or supplemented by water or buffer solution sothat the volume of the batch changes only minimally, if at all. In otherwords, the dye concentration remains constant or substantially constant.The dye concentration of the permeate does not change by more than 20%in a preferred embodiment, by not more than 10% in particularlypreferred processes and by not more than 5% in very particularlypreferred processes.

Following this diafiltration or ultrafiltration, the dye solution isbrought to the desired concentration by concentrating.

The membranes used in the process of the present invention are TFM™membranes, for example the G10, G20, G50 or DL5 membranes from GEOsmonics Desal (GE Osmonics Inc., 5951 Clearwater Drive, Minnetonka,Minn. 55343, United States), of which the DL5 membrane is particularlypreferred.

In a further, preferred version, the counterions of the cationic dye areexchanged, or further anions added, prior to diafiltration. The newlyadded anions mean that the original anions are easily removable throughultrafiltration or diafiltration. The counterions of the cationicfunctions are exchanged by halides in a particularly preferredembodiment and by chloride in a very particularly preferred embodiment.

The present invention further provides for the production of stableliquid formulations of anionic dyes by ultrafiltration of the aqueoussolution or suspension of the crude dye.

Ultrafiltration or diafiltration of the reaction solution, which isobtained as per the examples of WO 02/062902, although the dyestuff isnot isolated, can be used to render the reaction solution free offurther, undesirable additions. Free of undesirable additions is to beunderstood as meaning in particular that, post ultrafiltration ordiafiltration, the solutions comprise less than one % by weight andpreferably less than 0.5% by weight of further materials. Undesirablefurther materials are in particular inert salts and electrolytes which,having been used to neutralize and/or salt the dye out, come from thesynthesis stage and are carried along in the synthesis solution orsuspension, such as alkali metal or alkaline earth metal salts, forexample ammonium, magnesium chloride, magnesium sulphate, magnesiumbisulphate, sodium chloride, sodium sulphate, sodium bisulphate,potassium chloride, potassium sulphate or potassium bisulphate,especially sodium chloride.

This is followed by the addition of the required amount of organic acid.In principle, the organic acid can also be added before or during theultrafiltration or diafiltration.

As well as the water-soluble, organic acids identified, the dyesolutions of the present invention may comprise biocides.

Any biocide is suitable. But preference is given to biocides having FDAapproval. Any biocide capable of controlling the growth of Gram-positiveor Gram-negative bacteria, yeasts or fungi can be used in the solutionsof the present invention. Suitable biocides are for example 3-thiazolonederivatives, which are for example alkylated and/or chlorinated or usedas mixtures. Typically, biocides are added in an amount of up to 0.15%by weight per ready-produced composition.

The concentrated solutions can also be diluted again with water beforethey are used for dyeing. The concentrated solutions can also be shadedwith further dyes before use. But the concentrated solutions can also beused for shading other dyes.

Dyes especially useful for shading or for being shaded include all dyeswhich the Colour Index identifies as C.I. Basic Red or C.I. Basic Brownor C.I. Basic Blue or C.I. Basic Violet, and especially one or more ofthe following dyes can be used for shading: C.I. Basic Brown 23 or C.I.Basic Red 12 or C.I. Basic Blue 1 or C.I. Basic Red 14 or C.I. BasicViolet 10 or C.I. Basic Blue 26.

Dyes of the formula (II) and/or of the formula (III) are similarlyuseful for shading or for being shaded.

The concentrated solutions can also be used for shading brown dyes ofthe formula (II), or the concentrated solutions can be shaded with dyesof the formula (II).

The dyes of the formula (II) have the following structure:

where B₁ and B₂ are independently —OH and NH₂ and D₃=H or a residue ofthe formula

andR₆, R₇, R₈ or R₉ are independently H or —SO₃H andM_(a) or M_(b) independently have the meanings of M₁ to M₁₀, with

-   -   and    -   R_(a) or R_(b) independently have the meanings of R₁ to R₅.

The dyes of the formula (II) are known per se and can be prepared asdescribed in DE3715066.

The concentrated solutions can also be used for shading brown dyes ofthe formula (III), or the concentrated solutions can be shaded with dyesof the formula (III).

The dyes of the formula (III) have the following structure:

where

-   -   R¹, R² or R³ are independently H, CH₃, C₂H₅, n-C₃H₇, i-C₃H₇,        n-C₄H₉, i-C₄H₉, sec-C₄H₉,    -   R^(n) is —C₂H₄—, —C₃H₆—, —CH(CH₃)CH₂— or —C₄H₆—    -   Y is hydrogen or nitro,    -   q is 1 or 2.

The dyes of the formula (III) are known and can be prepared as describedin EP162409 or EP1352928.

Shading can be effected in the ratios of 2% to 98% by weight (based onthe dye) of a dye of the formula (I) and 98% to 2% by weight (based onthe dye) of a shading dye, i.e. for example in the ratios 2.0/98.0;2.5/97.5; 12.5/87.5; 22.5/77.5; 32.5/67.5; 42.5/57.5; 50.0/50.0;57.5/42.5; 67.5/32.5; 77.5/22.5; 80.0/20.0; 87.5/12.5; 90.0/10.0;95.0/5.0; 97.5/2.5; or 98.0/2.0.

The concentrated dye solutions of the present invention are used inparticular, if appropriate after dilution with water, for dyeing andprinting paper, including board and card, these materials being dyeablefor example in the pulp, by coat or by dipping. In addition, such aliquid formulation can also be used for a continuous or batch dyeingprocess for textile materials, especially cellulose. The concentrateddye solutions of the present invention can be used as a base forproducing inkjet inks or other inks and combinations for the contactlessprinting of substrates such as paper or textiles. The formulations ofthe present invention can also be used without further modification forthe contactless printing of substrates such as paper or textiles.

The present invention further provides for the use of the presentinvention's dye preparations of anionic dyes for producing wood stainsfor staining solid wood or wood chippings or chipboards or wood fibreboards. Staining wood in form of beams, boards or finished objects likefurniture, parts of buildings is a preferred use of the wood stainsaccording to the invention. The application of the liquid formulationsaccording to the invention may be carried out over the whole or part ofthe wood's surface (to compensate for color defects in the wood orveneer). The liquid formulations according to the invention may be usedin water stains (main solvent water), solvent stains (ca. 30-95% organicsolvent), or chemical stains (which are generally water thinnable).

The examples which follow illustrate the invention. Parts in theexamples as well as in the application as a whole are by weight and %ages always weight % ages unless otherwise stated.

PREPARATION EXAMPLE 1

425 parts of isatoic anhydride are added gradually at 50° C. to amixture of 118 parts of pentaerythritol and 8.7 parts of sodiumcarbonate in 434 parts of N,N-dimethylacetamide. The suspension isstirred for 2 hours and diluted with 4340 parts of water. This isfollowed by filtration, washing with water and drying at 60° C. underreduced pressure to obtain a white powder which is a mixture consistingof 4 components having the formulae (1a, 1b, 1c, 1d):

PREPARATION EXAMPLE 2

434 parts of the amino components of Example 1 are added to a mixture of1736 parts of ice, 781 parts of 30% HCl, 694 parts of acetic acid and260 parts of N,N-dimethylacetamide and are diazotized with 182 parts of4 N sodium nitrite solution. The temperature is maintained at 0-5° C. byaddition of 870 parts of ice. To the diazo solution obtained are added3281 parts of an approximately 20% aqueous solution of6-hydroxy-4-methyl-3-pyridonyl-3′-methylpyridinium chloride. The pH isadjusted to 3 at a temperature of 10-20° C. by addition of 130 parts of30% sodium hydroxide solution. After subsequent stirring for 1 hour, 50parts of Hyflo-Supercel filter earth are added before filtration througha porcelain suction filter with absorbent pad. The clear dye solutionobtained (9700 g; 8900 ml) is diafiltered in a laboratoryultrafiltration system having a DL5 membrane at 40-45° C. and a pressureof 15 bar until the conductivity in the permeate stays constant. In theprocess, the volume is kept substantially constant. This required about33 000 parts (ml) of demineralized water. The pH is maintained at4.0-4.5 during the ultrafiltration by addition of acetic acid. Theretentate is concentrated at a pressure of 12-15 bar to 5180 parts (g)and then admixed with 140 parts of acetic acid to obtain a solutionhaving a total dye content of about 20% by weight, consisting of thecomponents having the formulae (2a, 2b, 2c, 2d):

This solution (20.7% dye as chloride, 5.5% of acetic acid, 73.8% ofwater) dyes paper in a brilliant yellow hue (λ_(max.)=423 nm indimethylformamide/water), the concentrated solution being dilutable ifnecessary. The dyeings obtained have excellent wet fastnesses (to plainwater, alcohol, milk, soapy water, acetic acid, urine, etc.)

PREPARATION EXAMPLE A1

A mixture consisting of 7.7 g of 4-aminoacetanilide and 22.9 g of3-aminoacetanilide is diazotized with sodium nitrite by known methodsand to the mixture of the obtained diazonium salts 58.5 g of6-hydroxy-4-methyl-1-(3′-dimethylamino)propyl-3-pyridinio-2-pyridonebetaine base are added as coupling component and these are coupled byknown methods at a pH of 1.8-2.2.

The acetylamino group is then hydrolyzed with 57.5 g of 30% hydrochloricacid by known methods and thereupon the two aminoazo compounds arediazotized with 13.8 g of sodium nitrite by known methods and thediazonium salts obtained are coupled with 11 g of resorcinol at 0-5° C.

This provides a brown solution comprising 11.2 g of the dye of theformula

which dyes wood-containing paper in brown shades.

PREPARATION EXAMPLE A2

22.1 parts of ( 1/20 mol) of the compound of formula

are diazotized at 0-5° C. with 3.45 parts of sodium nitrite ( 1/20 mol)in a hydrochloric acid medium and coupled at a pH of 1-3 onto 5.4 partsof 1,3-diaminobenzene ( 1/20 mol) to obtain the dye of the formula (A2a)

Coupling 26.1 parts ( 1/20 mol) of the diazonium salt of the compound ofthe formula (A2b)

prepared by known methods by diazotization and coupling of1-amino-3-acetylaminobenzene-6-sulfonic acid onto pyridone andsubsequent saponification onto the dye of the formula (A2a) provides anisomer mixture of the dye of the formula:

(The possible coupling sites are marked by arrows).

This isomer mixture dyes wood-containing paper in brown shades.

Table 1 below indicates the construction of further dyes preparableaccording to Preparation Example A2. They conform to the formula

where B₁ and B₂ are independently —OH and NH₂ and D₃=H or a residue ofthe formula Table for M_(a) and M_(b) M₁ H M₂ —(CH₂)₃N(CH₃)₂ M₃—(CH₂)₂N(CH₂CH₃)₂ M₄

M₅

M₆

M₇

M₈

M₉

M₁₀ —(CH₂)₂NH₂

Table for R_(a) and R_(b) R₁ H R₂

R₃

R₄ —CN R₅

TABLE I Dye Position of azo bridge 1 H or Position of azo bridge 2 No.R_(a) M_(a) R₆ R₈ in ring B D₃ R_(b) M_(b) R₇ R₉ in ring C B₁ B₂ A3 R₂M₂ SO₃H H 3 H — — — H — OH OH A4 R₂ M₂ SO₃H H 4 H — — — H — OH NH₂ A5 R₂M₂ SO₃H H 4 H — — — H — NH₂ NH₂ A6 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ SO₃H H 3′ NH₂NH₂ A7 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ H H 4′ NH₂ NH₂ A8 R₂ M₂ SO₃H H 3 D₃ R₂ M₂H H 4′ NH₂ NH₂ A9 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ H H 4′ NH₂ OH A10 R₂ M₂ SO₃H H3 D₃ R₂ M₂ H H 4′ OH OH A11 R₂ M₂ SO₃H H 4 D₃ R₂ M₂ H H 3′ NH₂ NH₂ A12R₃ M₁ H H 3 D₃ R₂ M₂ SO₃H H 4′ NH₂ NH₂ A13 R₁ M₄ H H 3 D₃ R₂ M₅ SO₃H H4′ OH NH₂ A14 R₄ M₄ H H 3 D₃ R₂ M₆ SO₃H H 4′ NH₂ NH₂ A15 R₅ M₄ H H 3 D₃R₂ M₇ SO₃H H 4′ NH₂ NH₂ A16 R₂ M₂ SO₃H H 4 D₃ R₂ M₂ H H 3′ OH NH₂ A17 R₂M₂ SO₃H H 4 D₃ R₂ M₂ H H 3′ OH OH A18 R₂ M₈ SO₃H H 4 D₃ R₂ M₁ H H 3′ OHOH A19 R₂ M₈ SO₃H H 4 D₃ R₂ M₂ H H 3′ OH NH₂ A20 R₂ M₈ H H 4 D₃ R₂ M₄SO₃H H 3′ NH₂ NH₂ A21 R₂ M₉ H H 4 D₃ R₂ M₅ SO₃H H 3′ OH NH₂ A22 R₂ M₉ HH 3 D₃ R₄ M₃ SO₃H H 4′ OH OH A23 R₂ M₈ H H 3 D₃ R₅ M₄ SO₃H H 4′ NH₂ NH₂A24 R₂ M₃ H H 4 D₃ R₂ M₃ SO₃H H 3′ NH₂ NH₂ A25 R₂ M₂ H CH₃ 3 D₃ R₂ M₂SO₃H H 4′ OH OH A26 R₂ M₃ H CI 3 D₃ R₂ M₃ SO₃H H 4′ NH₂ NH₂ A27 R₂ M₂ HOCH₃, 3 D₃ R₂ M₄ SO₃H H 4′ NH₂ NH₂ A28 R₂ M₇ SO₃H H 4 D₃ R₂ M₇ H Cl 3′OH OH A29 R₂ M₈ SO₃H H 4 D₃ R₂ M₂ H CH₃ 3′ OH NH₂ A30 R₂ M₆ SO₃H H 4 D₃R₂ M₂ H OCH₃ 3′ NH₂ NH₂ A31 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ H H 3′ OH NH₂ A32 R₂M₂ SO₃H H 4 D₃ R₂ M₂ H H 4′ NH₂ NH₂ A33 R₂ M₂ SO₃H H 4 D₃ R₂ M₂ SO₃H H4′ NH₂ NH₂ A34 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ H H 3′ NH₂ NH₂ A33 R₂ M₂ SO₃H H 4D₃ R₂ M₂ H H 4′ NH₂ OH A34 R₂ M₂ SO₃H H 3 D₃ R₂ M₂ SO₃H H 4′ OH NH₂ A35R₂ M₁₀ SO₃H H 3 D₃ R₂ M₂ H H 3′ OH OH

PREPARATION EXAMPLE A36

Preparation of the diazo component: to 326 parts of isatoic anhydride in1000 parts of dioxane are added dropwise 187 parts ofdimethylaminoethanol at 60° C. Subsequent stirring for 1 hour isfollowed by concentrating in a water jet vacuum and distilling in a finevacuum. 402 parts of 2′-dimethylaminoethyl anthranilate pass over at160° C./0.1 Torr.

21 parts of 2′-dimethylaminoethyl anthranilate are dissolved in amixture of 50 parts of water, 25 parts of glacial acetic acid and 30parts of concentrated hydrochloric acid and, after cooling to 5° C.,admixed with 34.6 parts of a 23% aqueous solution of sodium nitriteadded dropwise. After three hours, excess nitrite is destroyed byaddition of sulphamic acid. A solution of 11 parts of resorcinol in 30parts of warm water is then added, the pH is raised with sodium acetateto pH 5 and the batch is stirred at room temperature overnight. Aftercooling to 0° C., the batch is gradually adjusted to pH 7 with 5Ncaustic soda. After 4 hours, the dye obtained is through crystallizedand can be filtered off with suction and washed with water. Air dryingyields 22 g of dye powder. The dye can be dissolved with glacial aceticacid and water to form a stable 20% liquid formulation. The dye dyespaper in a yellow hue. The hue is No. 4 on the Colour Index HueIndication Chart. The effluent is only minimally coloured. The dyedpapers can be bleached by means of hydrosulphite. The dissolved compoundconforms to the formula

PREPARATION EXAMPLE A37

Preparation of the diazo component: to 326 parts of isatoic anhydride in1000 parts of dioxane are added dropwise 187 parts ofdimethylaminoethanol at 60° C. Subsequent stirring for 1 hour wasfollowed by solvent removal in a vacuum and distilling 402 parts of2′-dimethylaminoethyl anthranilate passed over at 160° C./0.1 Torr.

275 parts of 2′-dimethylaminoethyl anthranilate were dissolved in amixture of 190 parts of water and 230 parts of methanesulphonic acidand, after cooling to 5° C., admixed with 150 parts of a 40% aqueoussolution of sodium nitrite added dropwise. After three hours, excessnitrite was destroyed by addition of sulphamic acid. A solution of 44parts of resorcinol in 160 parts of water was then added, and the batchwas raised to pH 5 with sodium acetate and subsequently stirred at roomtemperature for about 12 h to form a homogeneous solution. The dissolveddye conforms to the formula:

PREPARATION EXAMPLE 3

1.25 kg of the dye solution of Preparation Example 2 are mixed with 7.75kg of an approximately 10% liquid formulation of the dye of PreparationExample A1 at RT (=room temperature). This gives a stable dye solutionwhich dyes paper in a yellowish brown hue (λ_(max.)=433 nm inwater/acetic acid).

PREPARATION EXAMPLE 4

4.2 kg of the dye solution of Preparation Example 2 are mixed with 2.5kg of the dye solution of Preparation Example A36 at RT. The stable dyesolution obtained dyes paper in a reddish yellow hue (λ_(max.)=450 nm inwater/acetic acid).

Drying Prescriptions

Dyeing Prescription A

70 parts of chemically bleached pinewood sulphite cellulose and 30 partsof chemically bleached birchwood sulphite cellulose are beaten into 2000parts of water in a hollander.

1.5 parts of the liquid dye preparation of Preparation Example 2 areadded to this stock. Paper is made therefrom after a mixing time of 20minutes. The absorbent paper obtained in this way has a yellow colour.

Dyeing Prescription B

1.5 parts of the liquid dye preparation of Preparation Example 2 areadded to 100 parts of chemically bleached sulphite cellulose beaten with2000 parts of water in a hollander. After mixing through for 15 minutes,customary sizing is effected using resin size and aluminium sulphate.Paper made from this material exhibits a yellow hue in each case.

Dyeing Prescription C

An absorbent web of unsized paper is pulled at 40-50° C. through anaqueous dye solution consisting of 95 parts of water and 5 parts of theinventive dye solution of Preparation Example 2.

Excess dye solution is squeezed by two rolls. The dried web of paper hasa yellow colour in each case.

The dye preparations of Preparation Examples 3, 4 and A1-A37 can be usedfor dyeing similarly to Prescriptions A to C.

Dyeing Prescription D

5 parts of the dye preparation of Preparation Example 2 are metered into4000 parts of softened water at room temperature. 100 parts of prewettedwoven cotton fabric are introduced into the bath, followed by heating tothe boil over 30 minutes. The bath is held at the boil for an hourduring which evaporated water is made good from time to time. The dyeingis then removed from the liquor, rinsed with water and dried. The dyeingobtained has a yellow colour.

The dye preparation of Preparation Examples 3, 4 and A1-A37 can be usedfor dyeing cotton in a similar manner.

Dyeing Prescription E

100 parts of freshly tanned and neutralized chrome grain leather aredrummed for 30 minutes in a float of 250 parts of water at 55° C. and0.5 part of the dye preparation made according to Preparation Example 2and are treated for a further 30 minutes in the same bath with 2 partsof anionic fatliquor based on sulphonated fish oil. The leathers areconventionally dried and finished. The leather obtained has a levelyellow hue.

Further low-affinity, vegetable-retanned leathers can likewise be dyedaccording to known methods.

Dyeing can be done in a similar manner with dyes of Preparation Examples3, 4 and A1-A37.

Use Example F

15 kg of wastepaper (woody), 25 kg of bleached groundwood and 10 kg ofunbleached sulphate pulp were beaten in a pulper to form a 3% aqueouspulp suspension. The pulp suspension was diluted to 2% in a dyeing vat.This suspension was then admixed in succession with 5% of kaolin and1.25 kg of a 5% acetic acid solution of the dye of Preparation Example2, reckoned on dry total fibre, by stirring. After 20 minutes the pulpin the mixing vat is admixed with 1% (based on absolutely dry fibre) ofa resin size dispersion. The homogeneous pulp suspension was adjustedwith alum to pH 5 on the paper machine just upstream of the headbox.

The paper machine was used to produce 80 g/m² of yellow bag paper with amachine finish.

Dyeing can be done in a similar manner with dyes of Preparation Examples3, 4 and A1-A37.

Use Example G

A dry stock containing 60% groundwood and 40% unbleached sulphite pulpis beaten with sufficient water and ground to 40 SR freeness in ahollander for the dry content to be just above 2.5% and then adjustedwith water to a dry content of exactly 2.5% for the high-density pulp.

200 parts of this high-density pulp are admixed with 5 parts of a 0.25%aqueous solution of the dye of Preparation Example 2, stirred for about5 min., admixed with 2% of resin size and 4% of alum, based on drystock, and again stirred for some minutes until homogeneous. Thematerial is diluted with about 500 parts of water to 700 parts by volumeand used in a known manner to prepare sheets of paper by drainage on asheet-former. These sheets of paper have a deep yellow colour.

Dyeing can be done in a similar manner with dyes of Preparation Examples3, 4 and A1-A37.

Use Example H

An ink composition for inkjet printing consists of

6 parts of the dye of Preparation Example 2,

20 parts of glycerol and

74 parts of water.

This ink composition was then used for printing paper, paperysubstrates, textile fibre materials and plastic film/sheet bytransferring the ink into the ink receptacle of a commercially availableinkjet printer and using it to produce a single-coloured test print onthe identified sheetlike materials.

Dyeing can be done in a similar manner with dyes of Preparation Examples3, 4 and A1-A37.

Use Example I

A batten of coniferous wood (European spruce) and a batten of leafy wood(beech) were each cut into pieces of about 5 cm and immersed for someminutes in a diluted (10 parts water and 1 part of the dye solutionaccording to example 2) dyestuff solution according to example 2 andafter drying for ten hours light brownish batten pieces were obtained.

Dyeing can be done in a similar manner with dyes of Preparation Examples3, 4 and A1-A37.

1. A concentrated aqueous dye solution comprising at least onecationizable dye, an organic acid and water, wherein the at least onecationizable dye is of the formula (I)

wherein each A is independently —NH— or —O—, B is a polyvalent group oratom, n′ and n″ are natural numbers and the sum total of n′ and n″ is≧2, m is a natural number ≧0, CC is a group having the formula (c₁) or(c₂)

wherein each R₁₀ is independently H; C₁₋₄alkyl; C₅₋₆cycloalkyl; phenyl,benzyl or phenylethyl, each R₁₀′ is independently H; —OH or C₁₋₄alkyleach T₁ is independently H; —CN; —COOR₁₅; CONR₁₆R₁₇; SO₂NR₁₆R₁₇;

G is H; —R₁₁NHR₁₂ or —R¹¹NR₁₃R₁₄ where R₁₁ is C₁₋₆alkylene orC₂₋₆alkenylene, R₁₂, R₁₃ and R₁₄ are independently H; unsubstitutedC₁₋₆alkyl; C₂₋₆alkyl substituted by OH, CN or halogen; phenyl-C₁₋₃alkylwhere the phenyl radical is optionally singly, doubly or triplysubstituted by substituents selected from the group consisting ofchlorine, C₁₋₄alkyl and C₁₋₄alkoxy; unsubstituted C₅₋₆cycloalkyl orC₅₋₆cycloalkyl singly, doubly or triply substituted by C₁₋₄alkyl groups,R₁₅ is C₁₋₆alkyl radical or phenyl-C₁₋₃alkyl radical, R₁₆ and R₁₇ areindependently H or a C₁₋₄alkyl radical, R₁₈ is independently H or aC₁₋₄alkyl radical; —NR₁₆R₁₇—(CH₂)₂₋₄—NR₁₆R₁₇ or —CONR₁₆R₁₇, R₁₉ is aC₁₋₄alkyl radical or a hydroxy-C₁₋₄alkyl radical, R₂₀ is —S— or —O—, R₂₁is a hydrogen atom or a C₁₋₄alkyl radical, and An⁻ is a non-colouredanion, with the proviso that (i) the sum total of n′, n″ and m is lessthan the number of valences of B, (ii) when the sum total of n′ andn″=2, then m is ≧1, (iii) when the sum total of n′ and n″=3 and A=NH,then m is ≧1.
 2. A concentrated aqueous dye solution according to claim1 wherein the at least one cationizable dye is at least one dye of theformula (II)

where B₁ and B₂ are independently —OH or NH₂ and D₃=H or a residue ofthe formula

and R₆, R₇, R₈ and R₉ are independently H or —SO₃H and M_(a) and M_(b)are independently M₁ to M₁₀, wherein M₁ is H. M₂ is —(CH₂)₃N(CH₃)₂, M₃is —(CH₂)₂N(CH₂CH₃)₂, M₄ is

M₅ is

M₆ is

M₇ is

M₈ is

M₉ is

M₁₀ is —(CH₂)₂NH₂. and R_(a) or R_(b) are independently R₁ to R₅,wherein R₁ is H,

R₂ is

R₃ is R₄ is CN,

R₅ is or at least one dye of the formula (III)

Wherein R¹, R² or R³ are independently H, CH₃, C₂H₅, n-C₃H₇, i-C₃H₇,n-C₄H₉, i-C₄H₉, sec-C₄H₉, R^(n) is —C₂H₄—, —C₃H₆—, —CH(CH3)CH₂— or—C₄H₆— Y is hydrogen or nitro, q is 1 or 2 and An⁻ is a non-colouredanion.
 3. A concentrated aqueous dye solution according to claim 1wherein the organic acid is an organic acid of the formulaA′(—COOH)_(n), where A′ is C₁₋₁₂-alkanyl or C₁₋₁₂-alkenyl optionallyinterrupted by nitrogen atoms and/or oxygen atoms and optionallysubstituted by hydroxyl or NR′R″ (wherein R′ and R″ are independentlyC₁₋₆-alkanyl or C₁₋₆-alkenyl or C₁₋₆-hydroxyalkanyl orC₁₋₆-hydroxyalkenyl, or unsubstituted phenyl or hydroxyl- or sulphur- orC₁₋₁₈-alkanyl- or C₁₋₁₈-alkenyl-substituted phenyl and n is a naturalnumber of 1, 2 or
 3. 4. A concentrated aqueous dye solution according toclaim 1 wherein the concentrated aqueous dye solution comprises up to40% by weight of the at least one cationizable dye, from 0.5% to 25% byweight of the organic acid and is made up to 100% by weight with water.5. A process for producing a concentrated aqueous dye solution accordingto claim 1, comprising the step of pressing an aqueous solution orsuspension of at least one crude cationic dye of the formula (I) througha semipermeable membrane by applying a pressure to remove salts,synthesis by-products having molecular weights below 500, and a portionof the water.
 6. A process for producing a concentrated aqueous dyesolution according to claim 5, further comprising the step ofcontinuously or intermittently replacing or supplementing the permeatewith water or buffer solution so that the concentration of the at leastone crude cationic dye in the permeate does not change by more than 20%.7. A process for dyeing and/or printing cellulosic material, comprisingthe step of contacting the at least one concentrated aqueous dyesolution according to claim 1 with the cellulosic material.
 8. A processfor producing inks and formulations for contactless printing, comprisingthe step of combining at least one concentrated aqueous dye solutionaccording to claim 1, with at least one additional chemical and/orwater.
 9. A substrate that has been dyed or printed with a concentratedaqueous dye solution according to claim
 1. 10. A process according toclaim 7 wherein the cellulosic material is paper, board or card.
 11. Aprocess according to claim 8 wherein the contactless printing is inkjetprinting.
 12. A substrate dyed and/or printed by a process in accordancewith claim
 7. 13. An inkjet ink comprising the concentrated aqueous dyesolution according to claim 1.